Separation of new vat dyestuff isomers



Patented Nev; 22,1932

WILHELMIECKERT :OTTO (BRAUNSDORF, OF FRANKIEORT-ON-THE-MAIN-HOCHST,

GERMANY;ASSIGNORS T0 GENERAL aAIwTILINE WORKS, INC.,' OF YORK, N. Y},

oonrormmron or DELAWARE= PATE T oFFic snranarroiv oaas VAT nYEsrn'Frrsomnns 1 ."fidnrvuagi amina Mama Apr 11-4,; i930, :Seria1 No. 441,713,and in Germany May 10, 1929;.

Inthe U. S. Patent 1,588,451thereisf'de scribed a process whichcomprises,condensing a 1.4.5;8 naphthalenetetra-carboxylic acid compoundwith an ortho-diamine compound. The products thus obtainable (arevaluable dyestufls, although they are not of uniform constitution, butrather represent mixtures of isomeric dyestufis. When condensing, forinstance, 1.4.518-naphthalenetetra carboxylic acid withortho-phenylenediamine a mixture u of the two isomeric dyestufi's'ofthefollowing formulae: 1 i a is obtained. When" Condensing a substitute ed*ortho phenylene diamine with 1. {1.5;8- naphthalenetetra-carboxylicacid in many cases the same holds true, i. e. there is likewise obtaineda mixture of the two isomers.

The present invention relates to a process of separating the dyestuil'mixtures obtainable according to UQS. Patent 1,588,451 into their twocomponents." Another object of.

our invention is the purified dyestuffs obtainable accordingto ournewprocess.

We have found that the d estufi mixtures obtainable according to Patent1,588,- 451 can be separated into their components by means ofmono-chloro-aceticacid. In some cases it is possible to carry out theseparation by treating the-material at an el'e vated temperature withsuch a quantity. of mono-chloro-acetic acid as isnecessary'to dissolvethe more easily soluble component whereby the more diflicultly solubleisomer remains in the residue and the dissolved isomer may be recoveredby diluting or cooling the mono-chloracetic acid solution. In

most leases, however, this plain method is. not sulficient foreffecting" atcomplete separation:

of the isomericndyestufis. 'Inthese cases-We prefer to proceed'a'sfollows: 7 Weqtreat the Vdyestufl :mixturewith such a quantity: of[mono-chloro Qacetic acid as is sufficient to dissolve the greaterpartofthe dyestuff mixture bywhich step of our process. themore easilysoluble component is-completely goinginto solution'and slmultaneouslypasmaller part of the less easily soluble component is dissolved, wheres Vas asa the gresldue there remains the greater part .ofthe; lessieasilysoluble isomeric dyestufi'r, In ,order. to complete the. separation wemake -use offour discoverythat the acid salts of the'qisomeric dyestuffspossess more pronounced diflerences as-to' their solubilityinmono-chloro acetic acid as'the dyestuffs proper; e addv to thereaction mixture such a quantity. of antacid as; is necessary toformthe: ,acidsalts of the dyestuff components;

and treat-the filtrate as well as the residue with water, whereby fromthe residue the Thetacid'. saltaof: the less soluble" isomeric is; 1 Ldyestufl is thusprecipitated and/the separa" tion of the componentsiscompleted; After this we filter the solution from 'the residue l/Ve have"found that the acid salts formed i by acting'upon the dyestuffs; withhydro-j is to be treated with about 10 to 20 .partsof mono-chlorojaceticacid in order to dissolve the more" easily soluble component andsimultaneously a certain part of the less easily soluble dyestuii: Wehave foundit prefer- I able to carry outthe treatment with mono-, chloroacetic :acid at a temperature, of about 709G.1100 V The; followingexamples serveto illustrate the invention but they are-not intended'to1460 i limit it thereto, the parts being by x 10 parts of the mixture ofthe isomeric dyestufl's of the following compositions: a

obtainableby condensing a 1 .4. 5. 8-naphthalenetetra carboxylicacidwith'a 1.2-diaminobenzene according. to U. S. "Patent No. 1,588,451,are introduced into 200 parts of 'melted mono-chloro-acetic acid ata'temperature of abdut 70 C. to 809' C. A part'of the dyestu'fi? mixturedissolves to a red solution." Aftersome, time, such a quantity ofconcentrated hydrochloric acid is added slowly as 1 is necessary to formthe hydrochlorides of the dyestufi. components whereby themeltedinassassumes a little lighter hydrochloride 7 at once begins tocrystallize 7 fromthe solution.' When the precipitation:

' isfinishe d, the solidproduct is filtered by suction by means offilter stone, iwashed with it due 1 on the filter as well as thefiltrate is treatediiwith water at. an; elevated tempera ture' in orderto obtain the. separated dyestuffs. :From the yellowish brownresidue onthe filter there is obtained an orange dyestufi' 7 A andfrom thefiltrate a red dye Stufi -B They have the following formulae:. V I: 1

The orange dyestufi powder" dissolves in a monohydrate to a brownishsolution anddyes cotton from an oliveyat very brilliant orange tintsofexcellent :fastness properties. .The

red dyestufl dissolves in concentrated sul-' I furic acidto aredsolution and-dyes; cotton from anzolivevat bluish red tints of-veryodiastn ss pr pert es- V coloration. The -more difii'cultly soluble Whentreating the dyestufi mixture only with mono-chloro-acetic acid it maylikewise be separated into its components, though 7 not completely. r

Y I (2). By replacing inthe process ofv separarating the dyestufl'mixtures as described in Example 1 the hydrochloric acid by theequivalent quantity of sulfuric acid the separation is e'fi'ectedin a;verysimilar wayriwith 'formationfof the sulfates. -Also by'means of rhydrobromid'es: formed by causing, concentrated hydrobro nic acid toreact with the solution in monocliloro aceticacid of the dyestufi usedin Example l the separation of -the mixtures into their components maybe carried out in like) manner.

'( Th mi 'ure bf hei e i ilyelfi ;Q f he i?.c ow lne epmn t ns:

. R V v I wherein for the residue melted monio-chloro acetic acid andtheresiobtainable 1 lenetetra-car oxylic acid with ai4-methyl-l2-condensing a 1.4:.5.8-naphthar ot diaminobenzene can be separated in thesame 7 m nn r i to i rtw cmpcm -r Thence diflicultly soluble sulfateyields an gn'ange y stnfi fzthe feu -nine ormula I I R wherein R tadsforth r idue,

iii)

which dyesecotton froma' green hydro'sulfite tained by decompositionwith waterizared vat a clear orange red tint, whereas the dyedyestufiwhich has the following formula: stuif obtained from theiiltrate whichhas the; y v

about 1 hour the precipitated diflicultly soluble sulfate orhydro-chloride, respectively, is filtered by suction and washed with asmall quantity of melted mono'chloro-acetic acid. I rom} the residue onthwfilten there is'rohr fine following formula: r. Ri 14 \N Y i whereinR stands for the residue and dyes cotton trornjja green hydrosulfite Vatred tints", From the deep red filtrate there is precipitated by additionof water a y 1 7 H1 dark brownish violet precipitate which, when it isfiltered by suction and dried, represents; and which is obtained in i alarger yield than g ggf i owder of the followa the orange yfistufi,dyescotton insomewhat i 7 dull reddish-browntints.-*- F 7 (4) 10 partsof the mixture of the isomeric 9 dyestufi's of the followingcompositions:

i i" l i 06 i o o o a v 4 1 i r N k I I H: H Q i y i ton r m a ydro lfiv iB r- HaC CH: g H3O V OH; v id d M: I E15 (5) 100 partsoftheinixturegof theisomeric obtainable by condensing a1.4.5.8-naphthadyestuffs of the f gi p tmnsa lenetetra-carboxylic acidwith a 4.5-dimeth- 1 yl-1.2 diaminobenzene are dissolved partially y inabout parts of melted mono-chloro- 5 v T12 acetic acidandintoulthissolution are slowly 06 o 5 o I 1 introduced at atemperature of from 70 C. I to 100 C. 4, 3 parts ofconcentrated sulfuricacid or the equivalent quantity of hydrochlorio acid. After the meltedmass is stirred for 5 whereinR Staiitlg forthe residue 1 obtainable bycondensing a 1.4.5.8-naphthalenetetra-carboxylic acid with a1.2-dia-minonaphthalene are dissolved in about to times their weight ofmelted mono-chloro:

' acetic acid at about 7 9 C. transformed into the sulfates byadditionof40 parts of concen- V trated sulfuric acid and stirred at atemperaturevof from C. M C. until the precipitation of the morediflicultlysoluble part ofthe' mixture is finished. The precipitate isfiltered by suctionby means of a filter stone or asbestos, The residueyields a violet dyei g of the followingformula'z V y can;

y wherein R stands for the residue 4 0. e

whieh dyes cotton from a humane-est violet tints of good fastnessproperties. From wherein R stands for the residue is obtained which dyescotton from a hydrosulfite vat currant tints. v

(6) By separating into its components according to the process of thepreceding examples the mixture of the isomeric dyestufl of the followingcompositions:

e v v 1 v obtainable by condensing 1 .'4.5.;8-naphthalenetetra-"c arboxylic acid or. its :anhydride with a l-chloro-1;,2-diaminobenzenethere is obtained as difliculty soluble part of the mix ture a dyestufiof the following formula:

which dye-s eotton fr'om an olive green hydrosulfite vat s'car let tintsof 'good fastness rop- Il a erties. The mono-chloro acetic acid filtrateyields a 'dyestufi'of the following formula 1o v r o t id wherein Rstands for the resldue which dyes cotton from an olive green Vat I 5brown shades. 7 (7) The red brown mixture of the isomeric dyestuffs ofthe following compositions:

3, fa a' 04 04v" wherein R stands for the residne obtainable bycondensing a'1.4;5.8-naphthalenetetra-carboxylic acid and a4-bromo-1.2--

diaminobenzene can be separated in like manner into its components ofwhich the more diflicultly soluble one has the following formula:

whereinR stands for thefresidue j 'i and dyes cotton from "an olivegreen hydro-V sulfite vat copper red tints. The more readily solubleisomer obtained from the filtrate 7 has the following formnla';

wherein R stands for the residue and dyes cotton from an olive greenvat' brown shades. V a V r (8). When the mixtnreof the isomeric dye- Vstuffs of the following compositionszlg wherein R stands for there'sidneobtainable bg condensing a I1.4.5 8'-naphtha-Vf lenetetra-car no v " 30Y e rename isomer separates which has the following 01 I obtainable :by"condensing "a '1.4.5..8-naphtha+ v mula; r lenetetra-carboxylic acid orits anhydride with a t-methoxy-1.2-diaminobenzene, are introduced in -12times their weight of melted mono-chloro-acetie acid at a temperature ofabout 70 C. to 80C, and the whole is stirred for some time. 4-, 5 partsof sulfuric acid of 66 B. are then added drop by drop, stirring iscontinued for some time and the sulfate of the ditficultly solubledyestufi' component :0 no 7 p y 1 which has separated is filtered bysuction at v i V 1 T j i; 70 C. to C. Byj decomposition with V f 7 waterthere is obtainedfrom the filtrate a red- 7 3 7 dish browndyestuffs-which has the following whereingR stands'for the residueformula; I V L I v V r 1N0: 7 a v and which dyes cotton from an olivehydro: sulfite vat blue grey tints,-whereas the isomer 7 I obtained fromthe mono-'chloro-acetic acid a C I filtrate which has the followingformula: 9

wherein R stands for theresidue f I i i r :iot

' and dyes cotton from an olive green alkaline V wherein"R standsforthe'residue L hydrosulfiteVa-tred brown tints. The monochloro-aceticacid filtrate yields a violet brown dyestufi'of the following formula 3R I e i y a fiQ- n dyes cottonfrom an olive alkaline 'hydrosul- I r 0'fite vat grey tints. V V n i 9) 10 parts of the mixture of "theisomeric 'dyestufis oitheiollowing compositions:

QR, R oo E foo o 2\ j wherein R stands for the residue i V I 0 \R/VwhereinRistandsforthe residue e which dyes cotton from an oliye greenhydro '7 sulfite Vat Violetbrowntints of good fastne'ss i properties. r7' The mixture of the isomeric: dyestuffs wherein-R stand for theresidue f o of the following compositions: A i i 1 :q I

R R h 5 Y oo c o o 0H,- t

obtainahle bvrcondensing a '1.4.5 .8-naphtl1alenetetra carboxylic acidwith a3.5-dimethyl-- 1.2-diaminobenzene, are introducedat about 70 G.into 150 parts of melted mono-chloro- V acetic acid, the whole isstirred and such a 0 quantity of sulfuric acid is added asis neces- N/\N/ I N sary to form the sulfates of the dyestufi' l components.Whenworking up the residue I 15 and the filtrate thereare vobtainedtwodye- Wherem B S s f the d L, i i I stufls A and B of the "followingformulae:

i A V 'B '7 01m i V 0 c/ 04M obtainable by condensing a -ethoxyLZ-dil aaminobenze'ne" and a14.5.8-nihpthalenetetra- 1 V 7 2r carboxylic' acidwhich is very similar to the 9c in like manner into a redbrownldyest'ufi' A mixture used in Example 9, can be separated l e and aviolet brown] dyestufl' B'of the follow- 00 n 0 ing formulae: f N r V 30v a v wherein R stands for the residue: 7

of which A dyesthe cotton fiberfroman olive green hydro-sulfite vatreddish violet O tints and B from a likewise olive green vat 2 5/ \N/bordeaux red r V (12) 10 parts ofthe mixture of theisomeric 1 wherein Rstands for theresidue ,Q F F E f the composltlonsz' ljw 7 3m R 45 I h vI g OO/V\C// Q V I 1 I 7 6011355 n I t 1 V i 'Both of the componentsyield olive green vats same as the parentmaterial. 7 (11) 10 parts ofthemixture of the isomeric it g a v 1 a l v dyestuffs of the followingcompositions: o Y o r v V i A a R I V R N V N 55 i" \R/ Y\R/ 0K 0/ Q 0/wherein R stand for the residue:

G obtainable by condensing a =14.5. 81-napthalenetetrai carboxylic. acidwith a 4r-chloro-5 7 tained a red brown mixture of .the isomericdyestuffs of the following compositions:

bromo-l.2-diaminobenzene"are dispersed in about 10 times their weight ofmono-chloroacetic acid and converted into the sulfates at a temperatureof'between C. and C. by addition of tparts of sulfuric acid. After sometime the insoluble isomer of the dyestuff components is filtered bysuction and decomposed with water., It yields and brown dyestuff of thefollowing-formula:

bi Vi J I i which mixture can be separated by means of ponents and' intoa smaller part of thesur-c fate which is j'easily goingintosolution. Bydecomposing both the sulfates vwith water oft'he following formula:

which dyes cotton from ,an alkaline olive green hydrosulfite vat redbrown tints. From the mono-chloro-acetic acid'filtrate there is obtainedby decomposition with water a dyestuff of the following formula 1 i'4.5-.dich1oro 1,2+diaminobenzene there is obsulfuric acid into .a larer part of the di; ficultly'solublesulfateo the dyestuffs "comthere isobtained on" the onehand' a'idyes'tufi N N p v 0 l 77 N N 45' V 0! 01 rwhich dyes cotton scarlet tints of very V o 0 good fastness propertiesand on .the other \q I hand a product of the following formula; \R/ p ifC11 161"! 50 n wherein R stands for the residue:

'60 v r I Y which dyes cotton from an olive green hydrosulfite vat browntints. V p (13) condensing a 1 .4.5-.8-naphthalene- 6 tetra-carboxylicacid.or its anhydride with a which dyes cotton brown tints. Bothdyestufi's yield an olive green alkaline hydrosulfite vat.

We claim:

1. As new products the compounds of the following general formula:

wherein R represents a phenylene group sub stituted by alkyl, alkoxy,halogen or nitro', or a naphthylene group, the arylene groups beingbound in two adjacent positions to the nitrogen atoms, the said productsbeing capable of yielding a vat from which cotton ,is dyed very fasttints. 2. As new products the compounds of the following generalformula:

wherein R represents a phenylene group 7 which is substituted by atleast one substituby condensing a 1.4.5.8-naphthalene-tetraoarboxylicacid compound with an o-diamine compound.

4. The process which comprises heating such a dyestuff mixture as'isobtainable by condensing a 14.5.g-naphthalene-tetra:carboxylic acidcompound with an aromatic odiamine compound,witl1 such a quantity. of

mono-chloro-acetic acid as is-sufiicient to dissolve the greater part ofthe said dyestuif mixture, adding to the reaction mixture 8. quanwithwater.

tity of an acid capable of formingacid salts with the dyestuffcomponents, filteringand treating the filtrate as well as the residue 5.The process which comprises heating about 1 part by weight of one of thedyestufl mixtures obtainable by condensing a1.4.5.8-naphthalene-tetra-carboxylic acid compound with anaromatico-diamine' compound, with about 10-20 parts byweight of 0., adding about1-5 "partsby weight of con;

.175 mono-chloro-acetic acid at about 7 O C.

centrated sulfuric acid,:'filtering and treating f the filtrate as wellas the residue with water.

- 6. As a new product, the compound of the following probable formula:

containing two methyl groups in X- or Y positions,dyeing cotton from agreen hydrosulfite vat a clear orange red tint.

containing two chlorine atoms in X-or Y- positions dyeing cotton from anol ve green hydrosulfite vat scarlettints of good'fastness properties.

.7. As a new product, the compound of'the :1 following probable formula:g r

-. 18. Asa'new product, the compound. of the r following probableformula:

dyeing cotton fi'omnan olivg ren'hydrosfilfite vatv scarlet tints ofgood fastness' prop-o erties'g i o i 7 7 v In testlmony whereof,- weaflix our slgnatures. v V :5 P WILHELM ECKERT. 1OTTO BRAUNSDORF.

